Catalyst preparation method

• US 20020119890A1
• Filed: 02/26/2001
• Published: 08/29/2002
• Est. Priority Date: 12/04/2000
• Status: Active Grant

• Current Assignee: David James Schreck, Timothy T. Wenzel
• Original Assignee: Univation Technologies LLC (Dow, Inc.)
• Inventors: Wenzel, Timothy T., Schreck, David James
• Granted Patent: US 6,656,866 B2
• Time in Patent Office: Days
• US Class Current: 502/439
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/0258 Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 2531/48 Zirconium
• CPC Class Codes: B01J 2531/49 Hafnium
• CPC Class Codes: B01J 2531/56 Vanadium
• CPC Class Codes: B01J 31/14 of aluminium or boron
• CPC Class Codes: B01J 31/143 of aluminium
• CPC Class Codes: B01J 31/146 of boron
• CPC Class Codes: B01J 31/1616 Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts catalysts comprising molecular sieves B01J29/00
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 : Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/06 : Catalyst characterized by its size
• CPC Class Codes: C08F 4/65904 : in combination with another component of C08F4/64
• CPC Class Codes: C08F 4/65912 : in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 : supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 : two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 : two cyclopentadienyl rings being mutually bridged

Abstract

This invention relates to a method to prepare a supported catalyst system comprising preparing a combination comprising 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound and thereafter spray-drying the combination.

Claims

1. A method to prepare a supported catalyst system comprising preparing a combination comprising 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound and thereafter spray-drying the combination.

2. The method of claim 1 wherein the first catalyst compound is different from the second catalyst compound.

3. The method of claim 1 wherein the particle size and or shape of the first supported catalyst system is different from the particle size of the second supported catalyst system.

4. The method of claim 1 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.

5. The method of claim 1 wherein the combination to be spray dried is prepared by combining a two different supported activators with a catalyst compound.

6. The method of claim 1 wherein the combination to be spray dried is prepared by combining a two or more different supported catalyst compounds with an activator.

7. The method of claim 1 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.

8. The method of claim 1 wherein at least one of the activators is selected from the group consisting of:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,

methyl alumoxane,

and modified methyl alumoxane.

9. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.

10. The method of claim 1 wherein one or more of the catalyst compounds is selected from the group consisting of:

bis(cyclopentadienyl)titanium dimethyl,

bis(cyclopentadienyl)titanium diphenyl,

bis(cyclopentadienyl)zirconium dimethyl,

bis(cyclopentadienyl)zirconium diphenyl,

bis(cyclopentadienyl)haffium methyl and diphenyl,

bis(cyclopentadienyl)titanium di-neopentyl,

bis(cyclopentadienyl)zirconium di-neopentyl,

bis(cyclopentadienyl)titanium dibenzyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)vanadium dimethyl,

bis(cyclopentadienyl)titanium methyl chloride,

bis(cyclopentadienyl)titanium ethyl chloride,

bis(cyclopentadienyl)titanium phenyl chloride,

bis(cyclopentadienyl)zirconium methyl chloride,

bis(cyclopentadienyl)zirconium ethyl chloride,

bis(cyclopentadienyl)zirconium phenyl chloride,

bis(cyclopentadienyl)titanium methyl bromide,

cyclopentadienyl titanium trimethyl,

cyclopentadienyl zirconium triphenyl,

cyclopentadienyl zirconium trineopentyl,

cyclopentadienyl zirconium trimethyl,

cyclopentadienyl hafnium triphenyl,

cyclopentadienyl hafnium trineopentyl,

cyclopentadienyl hafnium trimethyl,

pentamethylcyclopentadienyl titanium trichloride,

pentamethylcyclopentadienyl titanium trichloride;

bis(indenyl)titanium diphenyl or dichloride,

bis(methylcyclopentadienyl)titanium diphenyl or dihalide,

bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;

dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride,

methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride,

methylenedicyclopentadienyl titanium diphenyl or dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)hafniium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)hafnium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride,

racemic-ethylene bis(1-indenyl)zirconium(W)dichloride,

racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride,

racemic-ethylene bis(1-indenyl)hafnimn(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafiium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)hafaium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride,

racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride,

indenyl zirconium tris(diethylcarbamate),

indenyl zirconium tris(pivalate),

indenyl zirconium tris(p-toluate),

indenyl zirconium tris(benzoate), (1-methylindenyl)zirconium tris(pivalate),

(2-methylindenyl)zirconium tris(diethylcarbamate),

(methylcyclopentadienyl)zirconium tris(pivalate),

cyclopentadienyl tris(pivalate),

(pentamethylcyclopentadienyl)zirconium tris(benzoate),

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

(indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and

(indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.

11. The method of claim 1 wherein the particle size and or shape of the first supported catalyst system is different from the particle shape of the second supported catalyst system.

12. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

bis(N-hexyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)di(bis(dimethylamide));

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;

(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)trichloride.

13. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:

[(2,4,6-(CH₃)₃C₆H₂)NCH₂CH₂]₂NH}MBz₂ (where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).

15. The composition of claim 14 wherein the first catalyst compound is different from the second catalyst compound.

16. The composition of claim 14 wherein the particle size and or shape of the first supported catalyst system is different from the particle size and or shape of the second supported catalyst system.

17. The composition of claim 14 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.

18. The composition of claim 14 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.

19. The composition of claim 14 wherein at least one of the activators is selected from the group consisting of:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,

methyl alumoxane,

and modified methyl alumoxane.

20. The composition of claim 14 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.

21. The composition of claim 14 wherein one or more of the catalyst compounds is selected from the group consisting of:

bis(cyclopentadienyl)titanium dimethyl,

bis(cyclopentadienyl)titanium diphenyl,

bis(cyclopentadienyl)zirconium dimethyl,

bis(cyclopentadienyl)zirconium diphenyl,

bis(cyclopentadienyl)haffium methyl and diphenyl,

bis(cyclopentadienyl)titanium di-neopentyl,

bis(cyclopentadienyl)zirconium di-neopentyl,

bis(cyclopentadienyl)titanium dibenzyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)vanadium dimethyl,

bis(cyclopentadienyl)titanium methyl chloride,

bis(cyclopentadienyl)titanium ethyl chloride,

bis(cyclopentadienyl)titanium phenyl chloride,

bis(cyclopentadienyl)zirconium methyl chloride,

bis(cyclopentadienyl)zirconium ethyl chloride,

bis(cyclopentadienyl)zirconium phenyl chloride,

bis(cyclopentadienyl)titanium methyl bromide,

cyclopentadienyl titanium trimethyl,

cyclopentadienyl zirconium triphenyl,

cyclopentadienyl zirconium trineopentyl,

cyclopentadienyl zirconium trimethyl,

cyclopentadienyl hafnium triphenyl,

cyclopentadienyl hafnium trineopentyl,

cyclopentadienyl hafnium trimethyl,

pentamethylcyclopentadienyl titanium trichloride,

pentamethylcyclopentadienyl titanium trichloride;

bis(indenyl)titanium diphenyl or dichloride,

bis(methylcyclopentadienyl)titanium diphenyl or dihalide,

bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;

dimethyl silydicyclopentadienyl titanium diphenyl or dichloride,

methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride,

methylenedicyclopentadienyl titanium diphenyl or dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)hafniium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)hafnium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride,

racemic-ethylene bis(1-indenyl)zirconium(IV)dichloride,

racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride,

racemic-ethylene bis(1-indenyl)hafnimn(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafiium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)hafaium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride,

racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride,

indenyl zirconium tris(diethylcarbamate),

indenyl zirconium tris(pivalate),

indenyl zirconium tris(p-toluate),

indenyl zirconium tris(benzoate), (1-methylindenyl)zirconium tris(pivalate),

(2-methylindenyl)zirconium tris(diethylcarbamate),

(methylcyclopentadienyl)zirconium tris(pivalate),

cyclopentadienyl tris(pivalate),

(pentamethylcyclopentadienyl)zirconium tris(benzoate),

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

(indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and

(indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.

22. The composition of claim 14 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

bis(N-hexyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)di(bis(dimethylamide));

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;

(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)trichloride.

23. The composition of claim 14 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:

[(2,4,6-(CH₃)₃C₆H₂)NCH₂CH₂]₂NH}MBz₂ (where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).

25. The process of claim 24 wherein the first catalyst compound is different from the second catalyst compound.

26. The process of claim 24 wherein the particle size and or shape of the first supported catalyst system is different from the particle size and or shape of the second supported catalyst system.

27. The process of claim 24 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.

28. The process of claim 24 wherein the combination to be spray dried is prepared by combining a two different supported activators with a catalyst compound.

29. The process of claim 24 wherein the combination to be spray dried is prepared by combining a two or more different supported catalyst compounds with an activator.

30. The process of claim 24 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.

31. The process of claim 24 wherein at least one of the activators is selected from the group consisting of:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,

methyl alumoxane,

and modified methyl alumoxane.

32. The process of claim 24 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.

33. The process of claim 24 wherein one or more of the catalyst compounds is selected from the group consisting of:

bis(cyclopentadienyl)titanium dimethyl,

bis(cyclopentadienyl)titanium diphenyl,

bis(cyclopentadienyl)zirconium dimethyl,

bis(cyclopentadienyl)zirconium diphenyl,

bis(cyclopentadienyl)haffium methyl and diphenyl,

bis(cyclopentadienyl)titanium di-neopentyl,

bis(cyclopentadienyl)zirconium di-neopentyl,

bis(cyclopentadienyl)titanium dibenzyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)vanadium dimethyl,

bis(cyclopentadienyl)titanium methyl chloride,

bis(cyclopentadienyl)titanium ethyl chloride,

bis(cyclopentadienyl)titanium phenyl chloride,

bis(cyclopentadienyl)zirconium methyl chloride,

bis(cyclopentadienyl)zirconium ethyl chloride,

bis(cyclopentadienyl)zirconium phenyl chloride,

bis(cyclopentadienyl)titanium methyl bromide,

cyclopentadienyl titanium trimethyl,

cyclopentadienyl zirconium triphenyl,

cyclopentadienyl zirconium trineopentyl,

cyclopentadienyl zirconium trimethyl,

cyclopentadienyl hafnium triphenyl,

cyclopentadienyl hafnium trineopentyl,

cyclopentadienyl hafnium trimethyl,

pentamethylcyclopentadienyl titanium trichloride,

pentamethylcyclopentadienyl titanium trichloride;

bis(indenyl)titanium diphenyl or dichloride,

bis(methylcyclopentadienyl)titanium diphenyl or dihalide,

bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;

dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride,

methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride,

methylenedicyclopentadienyl titanium diphenyl or dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)hafniium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl) (fluorenyl)hafnium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride,

racemic-ethylene bis(1-indenyl)zirconium(W)dichloride,

racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride,

racemic-ethylene bis(1-indenyl)hafnimn(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafiium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)hafaium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride,

racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride,

indenyl zirconium tris(diethylcarbamate),

indenyl zirconium tris(pivalate),

indenyl zirconium tris(p-toluate),

indenyl zirconium tris(benzoate), (1-methylindenyl)zirconium tris(pivalate),

(2-methylindenyl)zirconium tris(diethylcarbamate),

(methylcyclopentadienyl)zirconium tris(pivalate),

cyclopentadienyl tris(pivalate),

(pentamethylcyclopentadienyl)zirconium tris(benzoate),

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

(indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and

(indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.

34. The process of claim 24 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-dimectylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

bis(N-hexyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)di(bis(dimethylamide));

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;

(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)trichloride.

35. The process of claim 24 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:

[(2,4,6-(CH₃)₃C₆H₂)NCH₂CH₂]₂NH}MBz₂ (where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).

14. A composition of matter comprising a particle comprising a first supported catalyst system comprising a support, an activator and a metal catalyst compound and second supported catalyst system comprising a support, an activator and a metal catalyst compound.

24. A process to polymerize olefins comprising combining one or more olefins in a polymerization reactor with a supported catalyst system prepared by preparing a combination comprising 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound and thereafter spray-drying the combination.